US6489386B1 - Method and composition for improving gas barrier properties of polymeric containers and films - Google Patents

Method and composition for improving gas barrier properties of polymeric containers and films Download PDF

Info

Publication number
US6489386B1
US6489386B1 US09/634,288 US63428800A US6489386B1 US 6489386 B1 US6489386 B1 US 6489386B1 US 63428800 A US63428800 A US 63428800A US 6489386 B1 US6489386 B1 US 6489386B1
Authority
US
United States
Prior art keywords
formula
defined above
acid
barrier
hydroxybenzoic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US09/634,288
Inventor
Irene Greenwald Plotzker
Thomas Michael Ford
Kenneth George Sharp
Samuel Tacitus D'Arcangelis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US09/634,288 priority Critical patent/US6489386B1/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to APAP/P/2002/002394A priority patent/AP1458A/en
Priority to MXPA02001457A priority patent/MXPA02001457A/en
Priority to DE60027726T priority patent/DE60027726T2/en
Priority to CA002378235A priority patent/CA2378235A1/en
Priority to DK00955416T priority patent/DK1204563T3/en
Priority to AU67627/00A priority patent/AU6762700A/en
Priority to KR1020027001770A priority patent/KR100629823B1/en
Priority to AT00955416T priority patent/ATE325048T1/en
Priority to TR2002/00382T priority patent/TR200200382T2/en
Priority to PT00955416T priority patent/PT1204563E/en
Priority to BR0013308-6A priority patent/BR0013308A/en
Priority to CNB008114269A priority patent/CN1191972C/en
Priority to JP2001516830A priority patent/JP4795592B2/en
Priority to IL14752300A priority patent/IL147523A0/en
Priority to EA200200250A priority patent/EA005321B1/en
Priority to ES00955416T priority patent/ES2262531T3/en
Priority to PCT/US2000/021777 priority patent/WO2001012521A1/en
Priority to EP00955416A priority patent/EP1204563B1/en
Priority to ARP000104182A priority patent/AR025238A1/en
Priority to IL147523A priority patent/IL147523A/en
Publication of US6489386B1 publication Critical patent/US6489386B1/en
Application granted granted Critical
Assigned to INVISTA NORTH AMERICA S.A.R.L. reassignment INVISTA NORTH AMERICA S.A.R.L. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: E. I. DU PONT DE NEMOURS AND COMPANY
Assigned to JPMORGAN CHASE BANK, N.A. reassignment JPMORGAN CHASE BANK, N.A. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: INVISTA NORTH AMERICA S.A.R.L. F/K/A ARTEVA NORTH AMERICA S.A.R.
Assigned to INVISTA NORTH AMERICA S.A.R.L. (F/K/A ARTEVA NORTH AMERICA S.A.R.L.) reassignment INVISTA NORTH AMERICA S.A.R.L. (F/K/A ARTEVA NORTH AMERICA S.A.R.L.) RELEASE OF U.S. PATENT SECURITY INTEREST Assignors: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT AND COLLATERAL AGENT (F/K/A JPMORGAN CHASE BANK)
Assigned to DEUTSCHE BANK AG NEW YORK BRANCH, AS COLLATERAL AGENT reassignment DEUTSCHE BANK AG NEW YORK BRANCH, AS COLLATERAL AGENT SECURITY AGREEMENT Assignors: INVISTA NORTH AMERICA S.A.R.L.
Assigned to E.I. DUPONT DE NEMOURS AND COMPANY reassignment E.I. DUPONT DE NEMOURS AND COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: INVISTA NORTH AMERICA S.A.R.L.
Assigned to INVISTA NORTH AMERICA S.A.R.L. reassignment INVISTA NORTH AMERICA S.A.R.L. RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: DEUTSCHE BANK AG NEW YORK BRANCH
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/138—Phenolates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/008—Additives improving gas barrier properties

Definitions

  • the present invention is a polymer composition and method for improving the gas barrier performance of polymeric containers and films, and particularly containers for food and beverages which are molded from thermoplastic polyester polymers. More particularly, the invention is a polymer composition and method for reducing the permeability of gases through molded polymeric containers, sheets and films by incorporating into the polymer from which the container, sheet or film is formed an effective amount of a barrier-enhancing additive of the type described herein.
  • the present invention and the inventive features described herein reside in the discovery of certain barrier-enhancing additives for thermoplastic polymers.
  • the invention is a polymer composition that contains one or more of the additives and a method for reducing gas permeability of shaped polymeric articles produced from such a composition, such articles being generally selected from containers, sheets and films.
  • the method comprises incorporating into the polymer an effective amount of a barrier-enhancing additive, or a mixture of barrier-enhancing additives, selected from the group consisting of:
  • R is C 1 -C 8 alkyl, benzyl, phenyl or naphthyl; Ar is substituted or unsubstituted phenylene or naphthalene; or formula (AA) where M is a cation such as, but not limited to, sodium, ammonium, tetraalkyl ammonium, potassium, calcium, magnesium or zinc;
  • R 1 is C 1 -C 8 alkyl, (CH 2 CH 2 O) k CH 2 CH 2 where k is 1 or more, benzyl, phenyl or naphthyl; or formula (BB) where M is as defined above.
  • R and Ar are as defined above; or formula (CC) where M is as defined above.
  • R 2 is C 1 -C 8 alkyl, (CH 2 CH 2 O) k CH 2 CH 2 where k is 1 or more, benzyl, phenyl or naphthyl; or formula (DD) where M is as defined above.
  • an effective amount i.e., the preferred range of barrier enhancing additive, is from 0.1% by wt. to 20% by wt. of the base polymer comprising the polymeric article.
  • the present invention resides in the discovery that oxygen, water vapor and carbon dioxide (CO 2 ) permeability values for shaped polymeric containers and films can be substantially reduced by incorporating into the base polymer from which the articles are formed from about 0.1% by wt. up to about 20% by wt. of a barrier-enhancing additive of the type defined herein.
  • CO 2 carbon dioxide
  • a uniform physical blend, or mixture is prepared comprising the base polymer and one or more barrier-enhancing additives in the desired concentrations.
  • composition is intended to mean a physical blend or mixture.
  • Water-sensitive base polymers such as, for example, polyesters should preferably be thoroughly dried by heating under air or nitrogen flow or vacuum as known to those experienced in the art.
  • the mixture is then heated and extruded or molded at a sufficiently high temperature to melt the base polymer and provide for sufficient mixing of the additive or mixture of additives within the base polymer matrix.
  • melt temperature ranges from about 255° C. to 300° C.
  • the composition thus produced comprises the barrier-enhancing additive (or mixture of such additives) substantially in its (their) original molecular form; that is, only small amounts of barrier-enhancing additive have been observed to react with the base polymer via trans-esterification or other reaction mechanism typical of the functional groups present. It is preferred to prepare and extrude or mold the polymer composition under conditions of relatively low temperature and processing residence time which thereby minimizes the opportunity for the barrier-enhancing additives to react with the base polymer. Best performance in terms of desirable mechanical properties of polymeric containers and films produced according to the invention is achieved when no more than about 10% of the gas barrier-enhancing additive has reacted with the base polymer. As a consequence of any reaction of a gas barrier-enhancing additive within the scope of the invention with a base polymer, the molecular weight of the starting base polymer may decrease.
  • gas barrier-enhancing additives found to be most suitable for carrying out the invention are selected from the group consisting of:
  • R is C 1 -C 8 alkyl, benzyl, phenyl or naphthyl; Ar is substituted or unsubstituted phenylene or naphthylene; or formula (AA) where M is a cation such as, but not limited to, sodium, ammonium, tetraalkyl ammonium, potassium, calcium, magnesium or zinc;
  • R 1 is C 1 -C 8 alkyl, (CH 2 CH 2 O) k CH 2 CH 2 where k is 1 or more, benzyl, phenyl or naphthyl; or formula (BB) where M is as defined above.
  • R and Ar are as defined above; or formula (CC) where M is as defined above.
  • R 2 is C 1 -C 8 alkyl, (CH 2 CH 2 O) k CH 2 CH 2 where k is 1 or more, benzyl, phenyl or naphthyl; or formula (DD) where M is as defined above.
  • R 3 is C 1 -C 8 alkyl, C 1 -C 8 dialkyl, (CH 2 CH 2 O) k CH 2 CH 2 , where k is 1 or greater, benzyl, phenyl or naphthyl, or formula (EE) where M is as defined above.
  • the above-defined barrier-enhancing additives can be obtained from commercial suppliers or they can be synthesized using established procedures.
  • Base polymers most suitable for use in practicing the invention comprise thermoplastic homopolymers, copolymers (both block and random), and blends of such thermoplastic polymers. Most suitable are polyester homopolymers and copolymers. Among suitable polyester base polymers are those polymers which contain structural units derived from one or more organic diacids (or their corresponding esters) selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids, hydroxybenzoic acids, hydroxynaphthoic acids, cyclohexane dicarboxylic acids, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecane dioic acid and the derivatives thereof, such as, for example, the dimethyl, diethyl, or dipropyl esters or acid chlorides of the dicarboxylic acids and one or more diols selected from ethylene glycol, 1,3-propane diol, nath
  • the polyester base polymer is polyethylene terephthalate (PET), which includes PET polymer which has been modified with from about 2 mole % up to about 5 mole % of isophthalate units.
  • PET polyethylene terephthalate
  • Such modified PET is known as “bottle grade” resin and is available commercially as Melinar® Laser+polyethylene terephthalate brand resin (E. I. du Pont de Nemours and Company, Wilmington, Del.).
  • PET will refer to commercially available “bottle grade” polyester resin.
  • Film samples are indicative of the improved gas barrier properties obtainable from the invention.
  • Such film samples were generated from physical blends of a base polymer and a selected additive from among those described herein, and the samples were either compression molded or extrusion cast using a co-rotating twin screw extruder with a slit die, typically having a 0.38 mm gap, a quench roll, and a vacuum port on the front barrel section, with barrel, adapter, and die temperatures set at 240° C. to 275° C. depending on the polymer composition being used. Melt temperatures were measured with a thermocouple, and, for samples prepared using a twin screw extruder, melt temperatures were typically about 15° C. to 20° C. above the set temperature.
  • a transfer line in which static mixers were installed within the line in place of a compounding screw, was used along with a slit die. Films were typically 0.05 to 0.25 mm thick. The thick films were subsequently stretched biaxially simultaneously to 3.5 ⁇ by 3.5 ⁇ using a Long stretcher at 90° C., 9000%/minute unless otherwise noted.
  • 26 g preforms were injection molded using a Nissei ASB 50 single stage injection stretch blow molding machine with barrel temperatures set at about 265° C. and with a total cycle time of about 30 seconds. The preforms were immediately blown into 500 mL round-bottomed bottles with a blow time of 5 seconds. All other pressure, time and temperature set-points were typical for commercially available PET bottle resin.
  • Tensile bars 1 ⁇ 8′′ thick were molded using a 6 oz. injection molding machine with the following machine set-up: barrel temp: 255° C., mold temp: 20° C./20° C., cycle time: 20 sec/20 sec, injection pressure: 5.5 MPa, RAM speed: fast, screw speed: 60 rpm, and back pressure: 345 kPa.
  • Oxygen permeability values were measured for each sample according to ASTM procedure D3985 at 30° C., 50% RH on an Ox-Tran 1000 instrument from Modem Controls, Inc. Carbon dioxide permeability was measured at 25° C. and 0% RH on a Permatran CIV instrument, also from Modern Controls, Inc. Water vapor permeability was measured at 37-38° C., 100% RH on a Permatran-W600 instrument, also from Modem Controls, according to ASTM procedure F1249.
  • Intrinsic viscosity values were determined from 0.4 wt % solution of polymers or polymer blends in a 1:1 (by weight) mixture of methylene chloride and trifluoroacetic acid at 20° C.
  • Films comprising commercially available PET resin (Melinar® Laser+PET brand resin) as the base polymer plus a barrier additive were prepared by a variety of methods as follows: melt pressing (M), extrusion compounding through a slit die (E), and transfer line mixing (T) into a slit die, and noted below in the table. Compositions are indicated in Table 1. After extrusion, films were simultaneously biaxially stretched to 3.5 ⁇ by 3.5 ⁇ at 90° C. and at a rate of 9000%/min. Oxygen permeation values (OPV) were measured according to ASTM procedure D3985 at 30° C., 50% relative humidity.
  • OOV Oxygen permeation values
  • control OPV is the mean of values for seven different samples, each run in duplicate; the standard deviation is 0.49.
  • control OPV is the mean of values for 27 different samples, each run in duplicate; the standard deviation is 0.41.
  • Films prepared from commercially available PET resin (Melinar® Laser+brand PET resin) which contained zero or nominally 2 wt % of the sodium salt of methyl 4-hydroxybenzoate were extruded using a twin screw extruder.
  • Oxygen permeability values were determined for both as-cast and biaxially stretched films, as in Ex. 1. Films were stretched to 3.5 ⁇ by 3.5 ⁇ at 9000%/min, 100° C.
  • the OPV for the stretched film containing the additive was 5.18 cc-mils/100 sq. in-24 hr-atm stretched, versus 6.56 for stretched PET film without an additive; the additive therefore produced a 26.6% improvement in oxygen barrier performance.
  • Poly(propylene terephthalate) (‘3GT’) films containing zero and nominally 3 wt % methyl 4-hydroxybenzoate (‘MHB’) were prepared using a twin screw extruder and a barrel setting of 240° C. Films containing no MHB and nominally 3 wt % MHB were stretched 3 ⁇ by 3 ⁇ at 55° C. and 53° C. respectively. Oxygen permeability values for the 3GT films containing MHB were 4.72 cc-mil/100 sq. in-24 hr-atm for cast film and 3.59 cc-mil/100 sq. in-24 hr-atm for stretched film, versus the 3GT control OPV values of 8.56 for as-cast film and 5.30 for stretched film.
  • ‘MHB’ Poly(propylene terephthalate)
  • Water vapor permeability at 38° C. for as-cast films containing MHB was 2.22 g-mil/100 sq. in-24 hr and 1.95 g-mil/100 sq. in-24 hr for stretched film, versus the 3GT control values of 3.50 for as-cast film and 2.24 for stretched film.
  • a blend of MHB with PET (IV 0.86) was prepared via twin-screw extrusion at 245° C.
  • the resulting blend which was a concentrate, had an IV of 0.86 dL/g, and contained 6.9% MHB by NMR analysis.
  • the blend was dried overnight at 100° C. under vacuum and combined with standard commercial PET bottle resin (IV 0.83 dL/g, dried 6 hours at 150° C.).
  • 26 g sample preforms were then injection molded using a Nissei ASB 50 single stage injection stretch blow molding machine, using barrel temperatures of about 265° C. and a total cycle time of approximately 30 seconds. The preforms were immediately blown into 500 mL round-bottomed bottles with a blow time of 5 seconds.
  • PET film containing 4 wt % MXD-6 6007 nylon Mitsubishi Gas Chemical Corp.
  • 3 wt % MHB was extruded along with a PET control film.
  • the films were biaxially stretched 3.5 ⁇ by 3.5 ⁇ as in Example 1.
  • the OPV for the film containing the additives was 2.59 cc-mils/100 sq. in-24 hr-atm, versus the control film's OPV of 7.14.
  • PET films containing 0 and 4.55 wt % of this diester were extruded and then stretched as in Example 1.
  • the OPV of the film containing the diester was 3.93 cc-mils/100 sq. in-24 hr-atm, and the OPV of the PET film without the diester was 7.32 cc-mils/100 sq. in-24 hr-atm.
  • An extruded PET film containing a nominal 3 wt % of this diamide and stretched as in Example 1 exhibited an OPV of 5.46 cc-mil/100 sq. in-24 hr-atm whereas a PET control film exhibited an OPV of 7.79.
  • a diester of HBA and triethylene glycol was synthesized from the reaction of stoichiometric mixtures of HBA and triethylene glycol in diphenyl ether with the catalyst butyl stannoic acid.
  • PET film containing 6.49 wt % of this diester (determined by NMR) was extruded and stretched as in Example 1.
  • the OPV for this film was 4.0 cc-mil/100 sq. in-24 hr-atm whereas a PET control film exhibited an OPV of 7.04.
  • a blend of 97 wt % dried PET resin (Melinar® Laser+brand PET resin) and 3 wt % methyl 4-hydroxybenzoate was mixed thoroughly and added to the hopper of a 6 oz. injection molding machine.
  • Standard 1 ⁇ 8′′ thick tensile bars were molded with the following machine set-up: barrel temp 255° C., mold temp: 20° C./20° C., cycle time: 20 sec/20 sec, injection pressure: 5.5 MPa, RAM speed: FAST, screw speed: 60 rpm, and back pressure: 345 kPa.
  • Intrinsic viscosity was measured on sections which were cut from the center of the bars using a 0.4% solution in 1:1 TFA: CH 2 Cl 2 at 19° C.
  • the I.V. was 0.73 dL/g vs. a control PET resin sample molded under identical conditions which had an I.V. of 0.73 dL/g.
  • the I.V. of the bottle from Example 4 containing 1.97 wt % MHB and prepared from a pre-compounded MHB/PET concentrate, was 0.464 dL/g, and the control PET bottle I.V. was 0.76 dL/g.
  • This example demonstrates that degradation of the polymer composition's molecular weight (as evidenced by I.V.) can be avoided by selection of appropriate processing conditions.
  • Laser+PET films containing 0 to 3.46 wt % MHB were prepared by extrusion compounding. Two of these were also biaxially stretched as in Example 1. Water vapor permeabilities (g-mil/100 sq. in-24 hr) at 38° C., 100% relative humidity are tabulated below.
  • Films of a copolymer of composition 7.4% poly(isosorbide terephthalate)-co-92.6% poly(ethylene terephthalate), prepared according to U.S. Pat. No. 5,959,066, containing 0 to 3.85 wt % MHB were prepared by extrusion compounding, then biaxially stretched 3.5 ⁇ by 3.5 ⁇ at 90° C. (95° C. for 0% MHB), 9000%/min. Oxygen permeabilities are tabulated below.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

A polymer composition and method for reducing the permeability of gases through molded polymeric containers and films by incorporating into the polymer from which the container or film is formed an effective amount of a barrier-enhancing additive, such as monoesters of hydroxybenzoic acid and hydroxynaphthoic acid.

Description

CROSS REFERENCE TO RELATED APPLICATION
This application claims priority benefit from U.S. provisional patent application No. 60/148,537 filed Aug. 12, 1999.
BACKGROUND OF THE INVENTION
The present invention is a polymer composition and method for improving the gas barrier performance of polymeric containers and films, and particularly containers for food and beverages which are molded from thermoplastic polyester polymers. More particularly, the invention is a polymer composition and method for reducing the permeability of gases through molded polymeric containers, sheets and films by incorporating into the polymer from which the container, sheet or film is formed an effective amount of a barrier-enhancing additive of the type described herein.
The addition of small amounts of molecular additives to a base polymer can result in antiplasticization of the polymer whereby the modulus of the polymer increases below its glass transition temperature and its barrier to gas permeability can improve. For example, Robeson describes the use of phenyl-2-naphthyl amine in polysulfone [Robeson, L. M.; Faucher, J. A., J. Polym. Sci., Part B 7, 35-40 (1969)] and various polychlorinated aromatic molecules in polycarbonate and in polyvinyl chloride [Robeson, L. M., Polym. Eng. Sci. 9, 277-81 (1969)]. Maeda and Paul [Maeda, Y.; Paul, D. R., J Polym. Sci., Part B: Polym. Phys. 25, 981-1003 (1987)] disclose the use of tricresyl phosphate in polyphenylene oxide to lower the sorption of carbon dioxide (and therefore its permeability). However, the need exists to improve the gas barrier performance of polymer resins of the type currently used for molded containers for food and beverages, and, in particular, poly(ethylene) terephthalate (PET) thermoplastic polyester polymers used for producing injection stretch blow molded bottles for packaging water, carbonated soft drinks and beer. Additives selected from 4-hydroxybenzoates and related molecules of the type described herein have not been suggested.
SUMMARY OF THE INVENTION
The present invention and the inventive features described herein reside in the discovery of certain barrier-enhancing additives for thermoplastic polymers. The invention is a polymer composition that contains one or more of the additives and a method for reducing gas permeability of shaped polymeric articles produced from such a composition, such articles being generally selected from containers, sheets and films.
The method comprises incorporating into the polymer an effective amount of a barrier-enhancing additive, or a mixture of barrier-enhancing additives, selected from the group consisting of:
(a) monoesters of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (A)
Figure US06489386-20021203-C00001
wherein R is C1-C8 alkyl, benzyl, phenyl or naphthyl; Ar is substituted or unsubstituted phenylene or naphthalene; or formula (AA) where M is a cation such as, but not limited to, sodium, ammonium, tetraalkyl ammonium, potassium, calcium, magnesium or zinc;
(b) diesters of hydroxybenzoic acid of the formula (B)
Figure US06489386-20021203-C00002
wherein Ar is as defined above, and R1 is C1-C8 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl; or formula (BB) where M is as defined above.
(c) monoamides of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (C)
Figure US06489386-20021203-C00003
wherein R and Ar are as defined above; or formula (CC) where M is as defined above.
(d) diamides of hydroxybenzoic acid of the formula (D)
Figure US06489386-20021203-C00004
wherein Ar is as defined above, and R2 is C1-C8 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl; or formula (DD) where M is as defined above.
(e) ester-amides of hydroxybenzoic acid of the formula (E)
Figure US06489386-20021203-C00005
where Ar is as defined above and R3 is C1-C8 alkyl, C1-C8 dialkyl, (CH2CH2O)kCH2CH2 where k is 1 or greater, benzyl, phenyl or naphthyl, or formula (EE) where M is as defined above. As used herein, an effective amount, i.e., the preferred range of barrier enhancing additive, is from 0.1% by wt. to 20% by wt. of the base polymer comprising the polymeric article.
Polymeric articles, and particularly extruded film or injection stretch blow molded polyester (e.g., PET) bottles, which contain one or more of the barrier-enhancing additives described herein, exhibit substantially reduced oxygen and carbon dioxide permeability values when measured according to ASTM D3985 and water vapor permeability values when measured according to ASTM F1249 in comparison to corresponding polymeric articles which contained no barrier-enhancing additives.
DETAILED DESCRIPTION OF THE INVENTION
The present invention resides in the discovery that oxygen, water vapor and carbon dioxide (CO2) permeability values for shaped polymeric containers and films can be substantially reduced by incorporating into the base polymer from which the articles are formed from about 0.1% by wt. up to about 20% by wt. of a barrier-enhancing additive of the type defined herein.
A uniform physical blend, or mixture, is prepared comprising the base polymer and one or more barrier-enhancing additives in the desired concentrations. As used herein with reference to the invention, the term “composition” is intended to mean a physical blend or mixture. Water-sensitive base polymers, such as, for example, polyesters should preferably be thoroughly dried by heating under air or nitrogen flow or vacuum as known to those experienced in the art. The mixture is then heated and extruded or molded at a sufficiently high temperature to melt the base polymer and provide for sufficient mixing of the additive or mixture of additives within the base polymer matrix. By way of example using PET, such melt temperature ranges from about 255° C. to 300° C. The composition thus produced comprises the barrier-enhancing additive (or mixture of such additives) substantially in its (their) original molecular form; that is, only small amounts of barrier-enhancing additive have been observed to react with the base polymer via trans-esterification or other reaction mechanism typical of the functional groups present. It is preferred to prepare and extrude or mold the polymer composition under conditions of relatively low temperature and processing residence time which thereby minimizes the opportunity for the barrier-enhancing additives to react with the base polymer. Best performance in terms of desirable mechanical properties of polymeric containers and films produced according to the invention is achieved when no more than about 10% of the gas barrier-enhancing additive has reacted with the base polymer. As a consequence of any reaction of a gas barrier-enhancing additive within the scope of the invention with a base polymer, the molecular weight of the starting base polymer may decrease.
The gas barrier-enhancing additives found to be most suitable for carrying out the invention are selected from the group consisting of:
(a) monoesters of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (A)
Figure US06489386-20021203-C00006
wherein R is C1-C8 alkyl, benzyl, phenyl or naphthyl; Ar is substituted or unsubstituted phenylene or naphthylene; or formula (AA) where M is a cation such as, but not limited to, sodium, ammonium, tetraalkyl ammonium, potassium, calcium, magnesium or zinc;
(b) diesters of hydroxybenzoic acid of the formula (B)
Figure US06489386-20021203-C00007
wherein Ar is as defined above, and R1 is C1-C8 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl; or formula (BB) where M is as defined above.
(c) monoamides of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (C)
Figure US06489386-20021203-C00008
wherein R and Ar are as defined above; or formula (CC) where M is as defined above.
(d) diamides of hydroxybenzoic acid of the formula (D)
Figure US06489386-20021203-C00009
wherein Ar is as defined above, and R2 is C1-C8 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl; or formula (DD) where M is as defined above.
(e) ester-amides of hydroxybenzoic acid of the formula (E)
Figure US06489386-20021203-C00010
where Ar is as defined above and R3 is C1-C8 alkyl, C1-C8 dialkyl, (CH2CH2O)kCH2CH2, where k is 1 or greater, benzyl, phenyl or naphthyl, or formula (EE) where M is as defined above.
The above-defined barrier-enhancing additives can be obtained from commercial suppliers or they can be synthesized using established procedures.
Base polymers most suitable for use in practicing the invention comprise thermoplastic homopolymers, copolymers (both block and random), and blends of such thermoplastic polymers. Most suitable are polyester homopolymers and copolymers. Among suitable polyester base polymers are those polymers which contain structural units derived from one or more organic diacids (or their corresponding esters) selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids, hydroxybenzoic acids, hydroxynaphthoic acids, cyclohexane dicarboxylic acids, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecane dioic acid and the derivatives thereof, such as, for example, the dimethyl, diethyl, or dipropyl esters or acid chlorides of the dicarboxylic acids and one or more diols selected from ethylene glycol, 1,3-propane diol, nathphalene glycol, 1,2-propanediol, 1,2-, 1,3-, and 1,4-cyclohexane dimethanol, diethylene glycol, hydroquinone, 1,3-butane diol, 1,5-pentane diol, 1,6-hexane diol, triethylene glycol, resorcinol, and longer chain diols and polyols which are the reaction products of diols or polyols with alkylene oxides.
In a preferred embodiment of the invention the polyester base polymer is polyethylene terephthalate (PET), which includes PET polymer which has been modified with from about 2 mole % up to about 5 mole % of isophthalate units. Such modified PET is known as “bottle grade” resin and is available commercially as Melinar® Laser+polyethylene terephthalate brand resin (E. I. du Pont de Nemours and Company, Wilmington, Del.). As used hereinafter in illustrating the invention, the term PET will refer to commercially available “bottle grade” polyester resin.
Preparation of Film and Container Samples
Film samples are indicative of the improved gas barrier properties obtainable from the invention. Such film samples were generated from physical blends of a base polymer and a selected additive from among those described herein, and the samples were either compression molded or extrusion cast using a co-rotating twin screw extruder with a slit die, typically having a 0.38 mm gap, a quench roll, and a vacuum port on the front barrel section, with barrel, adapter, and die temperatures set at 240° C. to 275° C. depending on the polymer composition being used. Melt temperatures were measured with a thermocouple, and, for samples prepared using a twin screw extruder, melt temperatures were typically about 15° C. to 20° C. above the set temperature. In a few instances as noted, a transfer line, in which static mixers were installed within the line in place of a compounding screw, was used along with a slit die. Films were typically 0.05 to 0.25 mm thick. The thick films were subsequently stretched biaxially simultaneously to 3.5× by 3.5× using a Long stretcher at 90° C., 9000%/minute unless otherwise noted.
For fabricating bottles, 26 g preforms were injection molded using a Nissei ASB 50 single stage injection stretch blow molding machine with barrel temperatures set at about 265° C. and with a total cycle time of about 30 seconds. The preforms were immediately blown into 500 mL round-bottomed bottles with a blow time of 5 seconds. All other pressure, time and temperature set-points were typical for commercially available PET bottle resin.
Tensile bars ⅛″ thick were molded using a 6 oz. injection molding machine with the following machine set-up: barrel temp: 255° C., mold temp: 20° C./20° C., cycle time: 20 sec/20 sec, injection pressure: 5.5 MPa, RAM speed: fast, screw speed: 60 rpm, and back pressure: 345 kPa.
Analytical Procedures
NMR Spectrometry
Samples for 1H NMR were dissolved in tetrachloroethane-d2 at 130° C. Spectra were acquired at 120° C. at 500 MHz.
Thermal Analysis
Differential Scanning Calorimetric data were acquired at 2°/min on a TA Instruments calorimeter.
Permeability
Oxygen permeability values (OPV) were measured for each sample according to ASTM procedure D3985 at 30° C., 50% RH on an Ox-Tran 1000 instrument from Modem Controls, Inc. Carbon dioxide permeability was measured at 25° C. and 0% RH on a Permatran CIV instrument, also from Modern Controls, Inc. Water vapor permeability was measured at 37-38° C., 100% RH on a Permatran-W600 instrument, also from Modem Controls, according to ASTM procedure F1249.
Intrinsic Viscosity
Intrinsic viscosity values were determined from 0.4 wt % solution of polymers or polymer blends in a 1:1 (by weight) mixture of methylene chloride and trifluoroacetic acid at 20° C.
EXAMPLES Example 1
Films comprising commercially available PET resin (Melinar® Laser+PET brand resin) as the base polymer plus a barrier additive were prepared by a variety of methods as follows: melt pressing (M), extrusion compounding through a slit die (E), and transfer line mixing (T) into a slit die, and noted below in the table. Compositions are indicated in Table 1. After extrusion, films were simultaneously biaxially stretched to 3.5× by 3.5× at 90° C. and at a rate of 9000%/min. Oxygen permeation values (OPV) were measured according to ASTM procedure D3985 at 30° C., 50% relative humidity. Weight percent of the additive in the resin was assayed by NMR; where such analysis was not possible, nominal values (i.e., amounts initially mixed into the resin) are noted. In each case, both in unstretched and stretched films, the OPV was lower in films which contained a barrier-enhancing additive according to the invention than typical PET values (Control values, Table 1). OPV units are cc-mils/100 sq. in-24 hr-atm.
TABLE 1
Pre-
Sam- pa- Wt % OPV: OPV:
ple ration* Additive (NMR) Unstretched Stretched
Con- E None 0 11.08** 7.23**
trol
A M Methyl 4- 2.48 7.07 3.48
hydroxybenzoate
B T Methyl 4- 5.74 3.76 3.56
hydroxybenzoate
C T Methyl 4- 3.49 7.14 3.69
hydroxybenzoate
D T Methyl 4- 1.55 8.17 4.70
hydroxybenzoate
E T Methyl 4- 0.66 5.91
hydroxybenzoate
F E Ethyl 4- 3.71 5.42 4.14
hydroxybenzoate
G E n-Propyl 4- 2.90 7.91 4.74
hydroxybenzoate
H E i-Propyl 4- 6.00 4.01
hydroxybenzoate (nominal)
I M Benzyl 4- 5.88 8.87 3.99
hydroxybenzoate (nominal)
J M Phenyl 4- 5.55 7.71 3.82
hydroxybenzoate (nominal)
K E Phenyl 5 8.49 4.47
hydroxy- (nominal)
naphthoate
*Preparation methods: E = extrusion compounded then extrusion through a slit die to make film; M = melt-pressed film; T = transfer line with static mixers then extrusion through a slit die to make film.
**For unstretched PET film, the control OPV is the mean of values for seven different samples, each run in duplicate; the standard deviation is 0.49. For stretched film, the control OPV is the mean of values for 27 different samples, each run in duplicate; the standard deviation is 0.41.
Example 2
Films prepared from commercially available PET resin (Melinar® Laser+brand PET resin) which contained zero or nominally 2 wt % of the sodium salt of methyl 4-hydroxybenzoate were extruded using a twin screw extruder. Oxygen permeability values were determined for both as-cast and biaxially stretched films, as in Ex. 1. Films were stretched to 3.5× by 3.5× at 9000%/min, 100° C. The OPV for the stretched film containing the additive was 5.18 cc-mils/100 sq. in-24 hr-atm stretched, versus 6.56 for stretched PET film without an additive; the additive therefore produced a 26.6% improvement in oxygen barrier performance.
Example 3
Poly(propylene terephthalate) (‘3GT’) films containing zero and nominally 3 wt % methyl 4-hydroxybenzoate (‘MHB’) were prepared using a twin screw extruder and a barrel setting of 240° C. Films containing no MHB and nominally 3 wt % MHB were stretched 3× by 3× at 55° C. and 53° C. respectively. Oxygen permeability values for the 3GT films containing MHB were 4.72 cc-mil/100 sq. in-24 hr-atm for cast film and 3.59 cc-mil/100 sq. in-24 hr-atm for stretched film, versus the 3GT control OPV values of 8.56 for as-cast film and 5.30 for stretched film. Water vapor permeability at 38° C. for as-cast films containing MHB was 2.22 g-mil/100 sq. in-24 hr and 1.95 g-mil/100 sq. in-24 hr for stretched film, versus the 3GT control values of 3.50 for as-cast film and 2.24 for stretched film.
Example 4
A blend of MHB with PET (IV 0.86) was prepared via twin-screw extrusion at 245° C. The resulting blend, which was a concentrate, had an IV of 0.86 dL/g, and contained 6.9% MHB by NMR analysis. The blend was dried overnight at 100° C. under vacuum and combined with standard commercial PET bottle resin (IV 0.83 dL/g, dried 6 hours at 150° C.). 26 g sample preforms were then injection molded using a Nissei ASB 50 single stage injection stretch blow molding machine, using barrel temperatures of about 265° C. and a total cycle time of approximately 30 seconds. The preforms were immediately blown into 500 mL round-bottomed bottles with a blow time of 5 seconds. All other pressure, time and temperature set-points were typical for standard PET bottle resin. A control set of bottles made only of the standard PET bottle resin (IV 0.83, dried 6 hours at 150° C.) was prepared under the same conditions. The oxygen permeation value for panels cut from bottles containing 1.97 wt % methyl 4-hydroxybenzoate (‘MHB’) was determined to be 3.69 cc-mils/100 sq. in-24 hr-atm versus 5.73 for a control PET bottle panel. Carbon dioxide permeation values were 9.65 cc-mil/100 sq. in-24 hr-atm. for the bottle with MHB and 14.62 for the control panel.
Example 5
Commercially available PET film containing 4 wt % MXD-6 6007 nylon (Mitsubishi Gas Chemical Corp.) and, nominally, 3 wt % MHB was extruded along with a PET control film. The films were biaxially stretched 3.5× by 3.5× as in Example 1. The OPV for the film containing the additives was 2.59 cc-mils/100 sq. in-24 hr-atm, versus the control film's OPV of 7.14.
Example 6
A diester of p-hydroxybenzoic acid (‘HBA’) (corresponding to Formula B where R1=CH2CH2) was synthesized from the reaction of stoichiometric mixtures of HBA and ethylene glycol in diphenyl ether with the catalyst butyl stannoic acid. PET films containing 0 and 4.55 wt % of this diester were extruded and then stretched as in Example 1. The OPV of the film containing the diester was 3.93 cc-mils/100 sq. in-24 hr-atm, and the OPV of the PET film without the diester was 7.32 cc-mils/100 sq. in-24 hr-atm.
Example 7
The benzamide of HBA (corresponding to Formula C where R=phenyl) was synthesized from the reaction of MHB with benzylamine. An extruded PET film containing a nominal 3 wt % of this benzamide and stretched as in Example 1 exhibited an OPV of 5.00 cc-mil/100 sq. in-24 hr-atm, vs. a PET control film which had an OPV of 6.94.
Example 8
The diamide of HBA (corresponding to Formula D where R1=CH2CH2) was synthesized from the reaction of 4-acetoxybenzoyl chloride with ethylene diamine, followed by basic hydrolysis of the acetate groups. An extruded PET film containing a nominal 3 wt % of this diamide and stretched as in Example 1 exhibited an OPV of 5.46 cc-mil/100 sq. in-24 hr-atm whereas a PET control film exhibited an OPV of 7.79.
Example 9
A diester of HBA and triethylene glycol was synthesized from the reaction of stoichiometric mixtures of HBA and triethylene glycol in diphenyl ether with the catalyst butyl stannoic acid. PET film containing 6.49 wt % of this diester (determined by NMR) was extruded and stretched as in Example 1. The OPV for this film was 4.0 cc-mil/100 sq. in-24 hr-atm whereas a PET control film exhibited an OPV of 7.04.
Example 10
A blend of 97 wt % dried PET resin (Melinar® Laser+brand PET resin) and 3 wt % methyl 4-hydroxybenzoate was mixed thoroughly and added to the hopper of a 6 oz. injection molding machine. Standard ⅛″ thick tensile bars were molded with the following machine set-up: barrel temp 255° C., mold temp: 20° C./20° C., cycle time: 20 sec/20 sec, injection pressure: 5.5 MPa, RAM speed: FAST, screw speed: 60 rpm, and back pressure: 345 kPa. Intrinsic viscosity was measured on sections which were cut from the center of the bars using a 0.4% solution in 1:1 TFA: CH2Cl2 at 19° C. The I.V. was 0.73 dL/g vs. a control PET resin sample molded under identical conditions which had an I.V. of 0.73 dL/g.
In contrast, the I.V. of the bottle from Example 4, containing 1.97 wt % MHB and prepared from a pre-compounded MHB/PET concentrate, was 0.464 dL/g, and the control PET bottle I.V. was 0.76 dL/g. This example demonstrates that degradation of the polymer composition's molecular weight (as evidenced by I.V.) can be avoided by selection of appropriate processing conditions.
Example 11
Laser+PET films containing 0 to 3.46 wt % MHB were prepared by extrusion compounding. Two of these were also biaxially stretched as in Example 1. Water vapor permeabilities (g-mil/100 sq. in-24 hr) at 38° C., 100% relative humidity are tabulated below.
Water Vapor Water Vapor
Permeability, Permeability,
MHB Content (wt %) As-Cast Film Stretched Film
0 4.31 2.43
0.56 3.87 —
1.91 3.42 1.69
3.46 2.93 —
Example 12
Films of Lexan® 134r polycarbonate, Ultem® 1000 polyetherimide (both manufactured by General Electric), and Radel® polyethersulfone (manufactured by Boedeker Plastics, Inc.) containing 0 or nominally 5 wt % n-propyl p-hydroxybenzoate (PHB) were melt-pressed at 260, 270, and 270° C., respectively. Oxygen permeabilities (OPV) at 30° C. are tabulated below.
OPV, no PHB
(cc-mil/100 sq. in. 24 OPV, nom.5 wt % PHB
Polymer hr) (cc-mil/100 sq. in. 24 hr)
Lexan ® 134r 232.5 138.7
polycarbonate
Ultem ® 1000 48.05 24.45
polyetherimide
Radel ® 89.79 52.11
polyethersulfone
Example 13
Films of a copolymer of composition 7.4% poly(isosorbide terephthalate)-co-92.6% poly(ethylene terephthalate), prepared according to U.S. Pat. No. 5,959,066, containing 0 to 3.85 wt % MHB were prepared by extrusion compounding, then biaxially stretched 3.5× by 3.5× at 90° C. (95° C. for 0% MHB), 9000%/min. Oxygen permeabilities are tabulated below.
MHB Wt % OPV (cc-mil/100 sq. in/24 hr-atm)
0 8.22
0.70 8.02
2.24 5.57
3.85 3.98

Claims (20)

What is claimed is:
1. A method for reducing gas permeability of shaped thermoplastic polymeric articles wherein the polymer from which the article is formed is selected from the group consisting of polyesters, polycarbonates, polyetherimides and polyethersulfones and wherein the method comprises the steps of: (1) incorporating into the polymer an amount of a barrier-enhancing additive or a mixture of barrier-enhancing additives effective to reduce gas permeability and selected from the group consisting of:
(a) monoesters of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (A)
Figure US06489386-20021203-C00011
wherein R is C1-C4 alkyl, benzyl, phenyl or naphthyl; Ar is substituted or unsubstituted phenylene or naphthylene; or formula (AA) where M is a cation such as, but not limited to, sodium, ammonium, tetraalkyl ammonium, potassium, calcium, magnesium or zinc;
(b) diesters of hydroxybenzoic acid of the formula (B)
Figure US06489386-20021203-C00012
wherein Ar is as defined above, and R1 is C1-C4 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl; or formula (BB) where M is as defined above;
(c) monoamides of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (C)
Figure US06489386-20021203-C00013
wherein R and Ar are as defined above; or formula (CC) where M is as defined above;
(d) diamides of hydroxybenzoic acid of the formula (D)
Figure US06489386-20021203-C00014
wherein Ar is as defined above, and R2 is C1-C4 alkyl (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl; or formula (DD) where M is as defined above; and
(e) ester-amides of hydroxybenzoic acid of the formula (E)
Figure US06489386-20021203-C00015
where Ar is as defined above and R3 is C1-C4 alkyl, C1-C8 dialkyl, (CH2CH2O)kCH2CH2 where k is 1 or greater, benzyl, phenyl or naphthyl, or formula (EE) where M is as defined above by first forming a physical mixture comprising the polymer and one or more of the gas barrier enhancing additives, (2) heating the mixture to a temperature sufficiently high to melt the polymer but low enough to maintain the one or more gas barrier enhancing additives substantially in its or their original molecular form, and (3) forming the article.
2. The method of claim 1 wherein the thermoplastic polymer is selected from thermoplastic homopolymers, random or block copolymers or a blend or blends of such homopolymers and copolymers.
3. The method of claim 2 wherein the thermoplastic homopolymer or random or block copolymer is a polyester homopolymer or copolymer.
4. A thermoplastic polymer composition comprising (1) a base polymer which is selected from the group consisting of polyesters, polycarbonates, polyetherimides and polyethersulfones, including their homopolymers, random or block copolymers and a blend or blends of such homopolymers and copolymers and (2) an amount of one or more gas barrier-enhancing molecular additives, or a mixture of such gas barrier-enhancing molecular additives, effective to reduce the gas permeability of the base polymer and selected from the group consisting of:
(a) monoamides of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (C)
Figure US06489386-20021203-C00016
wherein R and Ar are as defined above; or formula (CC) where M is as defined above;
(b) diamides of hydroxybenzoic acid of the formula (D)
Figure US06489386-20021203-C00017
wherein Ar is as defined above, and R2 is C1-C4 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl; or formula (DD) where M is as defined above; and
(c) ester-amides of hydroxybenzoic acid of the formula (E)
Figure US06489386-20021203-C00018
where Ar is as defined above and R3 is C1-C4 alkyl, C1-C8 dialkyl, (CH2CH2O)kCH2CH2 where k is 1 or greater, benzyl, phenyl or naphthyl, or formula (EE) where M is as defined above.
5. The polymer composition of claim 4 in which the base polymer is a polyester homopolymer or copolymer which contains structural units derived from one or more organic diacids or their corresponding esters selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids, hydroxybenzoic acids, hydroxynaphthoic acids, cyclohexane dicarboxylic acids, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecane dioic acid and the derivatives thereof which are the dimethyl, diethyl, or dipropyl esters or acid chlorides of the dicarboxylic acids and one or more diols selected from the group consisting of ethylene glycol, 1,3-propane diol, nathphalene glycol, 1,2-propanediol, 1,2-, 1,3-, and 1,4-cyclohexane dimethanol, diethylene glycol, hydroquinone, 1,3-butane diol, 1,5-pentane diol, 1,6-hexane diol, triethylene glycol, resorcinol, and long chain diols and polyols which are the reaction products of diols or polyols with alkylene oxides, and the gas barrier-enhancing molecular additive or mixture of such gas barrier-enhancing molecular additives are present in the polymer composition at a total concentration of from 0.1% by wt. up to about 20% by wt of the composition.
6. The polymer composition of claim 4 in which the polyester homopolymer copolymer is polyethylene terephthalate.
7. An article of manufacture which is a sheet, a film or a container which is formed from the composition of claim 4.
8. A thermoplastic polymer composition comprising:
(1) a base polymer which is a polyester homopolymer or copolymer which contains structural units derived from one or more organic diacids or their corresponding esters selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids, hydroxybenzoic acids, hydroxynaphthoic acids, cyclohexane dicarboxylic acids, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecane dioic acid and the derivatives thereof which are the dimethyl, diethyl, or dipropyl esters or acid chlorides of the dicarboxylic acids and one or more diols selected from the group consisting of ethylene glycol, 1,3-propane diol, naphthalene glycol, 1,2-propanediol, 1,2-, 1,3-, and 1,4-cyclohexane dimethanol, diethylene glycol, hydroquinone, 1,3-butane diol, 1,5-pentane diol, 1,6-hexane diol, triethylene glycol, resorcinol, and long chain diols and polyols which are the reaction products of diols or polyols with alkylene oxides, and the gas barrier-enhancing molecular additive or mixture of such gas barrier-enhancing molecular additives are present in the polymer composition at a total concentration of from 0.1% by wt. up to about 20% by wt. of the composition; and
(2) an amount of a gas barrier-enhancing molecular additive or mixture of such gas barrier-enhancing molecular additives effective to reduce gas permeability of the base polymer and selected from the group consisting of:
(a) monoesters of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (A)
Figure US06489386-20021203-C00019
wherein R is C1-C4 alkyl, benzyl, phenyl or naphthyl; Ar is substituted or unsubstituted phenylene or naphthylene; or formula (AA) where M is a cation such as, but not limited to, sodium, ammonium, tetraalkyl ammonium, potassium, calcium, magnesium or zinc; and
(b) diesters of hydroxybenzoic acid of the formula (B)
Figure US06489386-20021203-C00020
wherein Ar is as defined above, and R1 is C1-C4 alkyl, (CH2CH2O)kCH2CH2.where k is 1 or more, benzyl, phenyl or naphthyl; or formula (BB) where M is as defined above.
9. The polymer composition of claim 8 in which the polyester homopolymer or copolymer is polyethylene terephthalate.
10. The method of claim 1 wherein the article is selected from the group consisting of containers, sheets and films and wherein no more than about 10% of the one or more barrier-enhancing additives reacts with the polymer.
11. A shaped thermoplastic polymeric article comprising a base polymer having physically incorporated therein an amount of one or more barrier-enhancing additives effective to reduce permeability of the shaped article to gases when compared to the shaped article not having the one or more barrier-enhancing additives incorporated therein, wherein the one or more barrier-enhancing additives are selected from the group consisting of:
(a) monoesters of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (A)
Figure US06489386-20021203-C00021
wherein R is C1-C4 alkyl, benzyl, phenyl or naphthyl; Ar is substituted or unsubstituted phenylene or naphthylene; or formula (AA) where M is a cation such as, but not limited to, sodium, ammonium, tetraalkyl ammonium, potassium, calcium, magnesium or zinc;
(b) diesters of hydroxybenzoic acid of the formula (B)
Figure US06489386-20021203-C00022
wherein Ar is as defined above, and R1 is C1-C4 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl; or formula (BB) where M is as defined above;
(c) monoamides of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (C)
Figure US06489386-20021203-C00023
wherein R and Ar are as defined above; or formula (CC) where M is as defined above;
(d) diamides of hydroxybenzoic acid of the formula (D)
Figure US06489386-20021203-C00024
wherein Ar is as defined above, and R2 is C1-C4 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl; or formula (DD) where M is as defined above; and
(e) ester-amides of hydroxybenzoic acid of the formula (E)
Figure US06489386-20021203-C00025
where Ar is as defined above and R3 is C1-C4 alkyl, C1-C8 dialkyl, (CH2CH2O)kCH2CH2 where k is 1 or greater, benzyl, phenyl or naphthyl, or formula (EE) where M is as defined above.
12. The shaped thermoplastic polymeric article of claim 11 wherein the thermoplastic base polymer is selected from the group consisting of polyesters, polycarbonates, polyetherimides and polyethersulfones and the one or more barrier-enhancing additives are incorporated therein by (i) forming a physical mixture comprising the base polymer and one or more of the gas barrier-enhancing additives, (ii) heating the mixture to a temperature sufficiently high to melt the base polymer but low enough to maintain the one or more barrier-enhancing additives substantially in its or their original molecular form, and (iii) forming the article.
13. The shaped thermoplastic polymeric article of claim 12 wherein no more than about 10% of the one or more barrier-enhancing additives reacts with the base polymer.
14. The shaped thermoplastic polymeric article of claim 13 which is a molded bottle wherein the base polymer is a polyester homopolymer or copolymer.
15. The molded bottle of claim 14 wherein the polyester homopolymer or copolymer comprises polyethylene terephthalate.
16. A blow molded thermoplastic polymeric bottle comprising a base polymer having incorporated therein an amount of one or more barrier-enhancing additives that is effective to reduce permeability of the molded bottle to oxygen and carbon dioxide gases when compared to a molded thermoplastic polymeric bottle not having the one or more barrier-enhancing additives incorporated therein, wherein the one or more barrier-enhancing additives are selected from the group consisting of:
(a) monoesters of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (A)
Figure US06489386-20021203-C00026
wherein R is C1-C4 alkyl, benzyl, phenyl or naphthyl; Ar is substituted or unsubstituted phenylene or naphthylene; or formula (AA) where M is a cation such as, but not limited to, sodium, ammonium, tetraalkyl ammonium, potassium, calcium, magnesium or zinc;
(b) diesters of hydroxybenzoic acid of the formula (B)
Figure US06489386-20021203-C00027
wherein Ar is as defined above, and R1 is C1-C4 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl; or formula (BB) where M is as defined above;
(c) monoamides of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (C)
Figure US06489386-20021203-C00028
wherein R and Ar are as defined above; or formula (CC) where M is as defined above;
(d) diamides of hydroxybenzoic acid of the formula (D)
Figure US06489386-20021203-C00029
wherein Ar is as defined above, and R2 is C1-C4 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl; or formula (DD) where M is as defined above; and
(e) ester-amides of hydroxybenzoic acid of the formula (E)
Figure US06489386-20021203-C00030
where Ar is as defined above and R3 is C1-C4 alkyl, C1-C8 dialkyl, (CH2CH2O)kCH2CH2 where k is 1 or greater, benzyl, phenyl or naphthyl, or formula (EE) where M is as defined above.
17. The blow molded thermoplastic polymeric bottle of claim 16 wherein the base polymer is selected from polyester homopolymers, random or block polyester copolymers and a blend or blends of such homopolymers and copolymers.
18. The blow molded thermoplastic polymeric bottle of claim 17 wherein the base polymer is bottle grade polyethylene terephthalate that has been modified with from about 2 mole % up to about 5 mole % of isophthalate units, and the barrier-enhancing additive is a monoester of hydroxybenzoic acid at a concentration of from about 0.01% by wt. to 6.0% by wt.
19. A method for producing a blow molded thermoplastic polymeric bottle comprising a base polymer selected from polyester homopolymers and copolymers having incorporated therein an amount of one or more barrier-enhancing additives that is effective to reduce permeability of the molded thermoplastic polymeric bottle to oxygen and carbon dioxide gases when compared to a molded thermoplastic polymeric bottle not having the one or more barrier-enhancing additives incorporated therein, wherein the one or more barrier-enhancing additives are selected from the group consisting of:
(a) monoesters of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (A)
Figure US06489386-20021203-C00031
wherein R is C1-C4 alkyl, benzyl, phenyl or naphthyl; Ar is substituted or unsubstituted phenylene or naphthylene; or formula (AA) where M is a cation such as, but not limited to, sodium, ammonium, tetraalkyl ammonium, potassium, calcium, magnesium or zinc;
(b) diesters of hydroxybenzoic acid of the formula (B)
Figure US06489386-20021203-C00032
wherein Ar is as defined above, and R1 is C1-C4 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl; or formula (BB) where M is as defined above;
(c) monoamides of hydroxybenzoic acid and hydroxynaphthoic acid of the formula (C)
Figure US06489386-20021203-C00033
wherein R and Ar are as defined above; or formula (CC) where M is as defined above;
(d) diamides of hydroxybenzoic acid of the formula (D)
Figure US06489386-20021203-C00034
wherein Ar is as defined above; and R2 is C1-C4 alkyl, (CH2CH2O)kCH2CH2 where k is 1 or more, benzyl, phenyl or naphthyl; or formula (DD) where M is as defined above; and
(e) ester-amides of hydroxybenzoic acid of the formula (E)
Figure US06489386-20021203-C00035
where Ar is as defined above and R3 is C1-C4 alkyl, C1-C8 dialkyl, (CH2CH2O)kCH2CH2 where k is 1 or greater, benzyl, phenyl or naphthyl, or formula (EE) where M is as defined above, said method comprising the steps of:
(i) forming a physical mixture comprising the base polymer and one or more of the gas barrier-enhancing additives;
(ii) heating and melt blending the mixture to a temperature sufficiently high to melt the base polymer but low enough to maintain the one or more barrier-enhancing additives substantially in its or their original molecular form; and
(iii) injection blow molding the bottle.
20. The method of claim 19 wherein the the base polymer is bottle grade polyethylene terephthalate that has been modified with from about 2 mole % up to about 5 mole % of isophthalate units, and the barrier-enhancing additive is a monoester of hydroxybenzoic acid at a concentration of from about 0.01% by wt. to 6.0% by wt of the composition.
US09/634,288 1999-08-12 2000-08-09 Method and composition for improving gas barrier properties of polymeric containers and films Expired - Fee Related US6489386B1 (en)

Priority Applications (21)

Application Number Priority Date Filing Date Title
US09/634,288 US6489386B1 (en) 1999-08-12 2000-08-09 Method and composition for improving gas barrier properties of polymeric containers and films
EA200200250A EA005321B1 (en) 1999-08-12 2000-08-10 Method and composition for improving gas barrier properties of polymeric containers and films
DE60027726T DE60027726T2 (en) 1999-08-12 2000-08-10 METHOD AND COMPOSITION FOR IMPROVING THE GAS BARRIER PROPERTIES OF POLYMER CONTAINERS AND FILMS
CA002378235A CA2378235A1 (en) 1999-08-12 2000-08-10 Method and composition for improving gas barrier properties of polymeric containers and films
DK00955416T DK1204563T3 (en) 1999-08-12 2000-08-10 Process and composition for improving gas barrier properties of polymeric containers and films
AU67627/00A AU6762700A (en) 1999-08-12 2000-08-10 Method and composition for improving gas barrier properties of polymeric containers and films
KR1020027001770A KR100629823B1 (en) 1999-08-12 2000-08-10 Methods and compositions for improving gas barrier properties of polymer containers and films
AT00955416T ATE325048T1 (en) 1999-08-12 2000-08-10 METHOD AND COMPOSITION FOR IMPROVING THE GAS BARRIER PROPERTIES OF POLYMERIC CONTAINERS AND FILMS
TR2002/00382T TR200200382T2 (en) 1999-08-12 2000-08-10 The method of improving the gas blocking properties of the films of polymer containers
PT00955416T PT1204563E (en) 1999-08-12 2000-08-10 METHOD AND COMPOSITION FOR IMPROVING THE PROPERTIES OF BARRIER TO GASES OF POLYMERIC CONTAINERS AND PELLETS
BR0013308-6A BR0013308A (en) 1999-08-12 2000-08-10 Method for reducing the permeability to gases from films, sheets and polymeric containers, polymer composition and manufactured article
CNB008114269A CN1191972C (en) 1999-08-12 2000-08-10 Method and composition for improving gas barrier properties of polymeric containers and films
JP2001516830A JP4795592B2 (en) 1999-08-12 2000-08-10 Methods and compositions for improving gas barrier properties of polymer containers and films
IL14752300A IL147523A0 (en) 1999-08-12 2000-08-10 Method and composition for improving gas barrier properties of polymeric containers and films
APAP/P/2002/002394A AP1458A (en) 1999-08-12 2000-08-10 Method and composition for improving gas barrier properties of polymeric containers and films.
ES00955416T ES2262531T3 (en) 1999-08-12 2000-08-10 METHOD AND COMPOSITION TO IMPROVE BARRIER PROPERTIES TO GASES OF CONTAINERS AND POLYMER FILMS.
MXPA02001457A MXPA02001457A (en) 1999-08-12 2000-08-10 Method and composition for improving gas barrier properties of polymeric containers and films.
EP00955416A EP1204563B1 (en) 1999-08-12 2000-08-10 Method and composition for improving gas barrier properties of polymeric containers and films
PCT/US2000/021777 WO2001012521A1 (en) 1999-08-12 2000-08-10 Method and composition for improving gas barrier properties of polymeric containers and films
ARP000104182A AR025238A1 (en) 1999-08-12 2000-08-11 METHOD FOR REDUCING GAS PERMEABILITY IN MOLDED ITEMS OF THERMOPLASTIC POLYMERS, COMPOSITION AND MOLDED ITEM OF THERMOPLASTIC POLYMER.
IL147523A IL147523A (en) 1999-08-12 2002-01-08 Method and composition for improving gas barrier properties of polymeric containers and films

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14853799P 1999-08-12 1999-08-12
US09/634,288 US6489386B1 (en) 1999-08-12 2000-08-09 Method and composition for improving gas barrier properties of polymeric containers and films

Publications (1)

Publication Number Publication Date
US6489386B1 true US6489386B1 (en) 2002-12-03

Family

ID=26845955

Family Applications (1)

Application Number Title Priority Date Filing Date
US09/634,288 Expired - Fee Related US6489386B1 (en) 1999-08-12 2000-08-09 Method and composition for improving gas barrier properties of polymeric containers and films

Country Status (20)

Country Link
US (1) US6489386B1 (en)
EP (1) EP1204563B1 (en)
JP (1) JP4795592B2 (en)
KR (1) KR100629823B1 (en)
CN (1) CN1191972C (en)
AP (1) AP1458A (en)
AR (1) AR025238A1 (en)
AT (1) ATE325048T1 (en)
AU (1) AU6762700A (en)
BR (1) BR0013308A (en)
CA (1) CA2378235A1 (en)
DE (1) DE60027726T2 (en)
DK (1) DK1204563T3 (en)
EA (1) EA005321B1 (en)
ES (1) ES2262531T3 (en)
IL (2) IL147523A0 (en)
MX (1) MXPA02001457A (en)
PT (1) PT1204563E (en)
TR (1) TR200200382T2 (en)
WO (1) WO2001012521A1 (en)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050100696A1 (en) * 2003-06-18 2005-05-12 Yu Shi Polyester composition for hot fill applications, containers made therewith, and methods
US20050118371A1 (en) * 2002-11-01 2005-06-02 The Coca-Cola Company PET copolymer composition with enhanced mechanical properties and stretch ratio, articles made therewith, and methods
US20050221036A1 (en) * 2004-04-01 2005-10-06 The Coca-Cola Company Polyester composition with enhanced gas barrier, articles made therewith, and methods
US20050260371A1 (en) * 2002-11-01 2005-11-24 Yu Shi Preform for low natural stretch ratio polymer, container made therewith and methods
WO2006112840A1 (en) * 2005-04-19 2006-10-26 The Coca-Cola Company Polyester composition with enhanced gas barrier, articles made therewith, and methods
US20060257602A1 (en) * 2005-05-11 2006-11-16 Yu Shi Low IV pet based copolymer preform with enhanced mechanical properties and cycle time, container made therewith and methods
US20060257603A1 (en) * 2005-05-11 2006-11-16 Yu Shi Preforms for preparing lightweight stretch blow molded pet copolymer containers and methods for making and using same
US20060275568A1 (en) * 2005-06-07 2006-12-07 The Coca-Cola Company Polyester Container with Enhanced Gas Barrier and Method
WO2007106302A1 (en) * 2006-03-01 2007-09-20 Invista Technologies S.Ar.L. Polymer composition with enhanced gas barrier, articles and methods
US20100044266A1 (en) * 2008-08-22 2010-02-25 E. I. Du Pont De Nemours And Company Polyester Blends
US20100143547A1 (en) * 2008-12-09 2010-06-10 Coca-Cola Company Pet Container And Compositions Having Enhanced Mechanical Properties And Gas Barrier Properties
US20100143546A1 (en) * 2008-12-09 2010-06-10 The Coca-Cola Company Container and composition for enhanced gas barrier properties
US20120006226A1 (en) * 2009-03-03 2012-01-12 Innogel Ag Starch foils and/or films and a method and use of a device for the production thereof
US8377530B2 (en) 2011-02-08 2013-02-19 Eastman Chemical Company Polyesters with low molecular weight additives for improved gas barrier properties
US20130231422A1 (en) * 2011-09-12 2013-09-05 Girish N. Deshpande Monolayer carbon dioxide barrier pet bottles
US10894625B1 (en) 2020-07-29 2021-01-19 Verre Vert, Inc. Lightweight polymer bottle for wine and spirits
US10899698B2 (en) 2010-10-26 2021-01-26 Ethox Chemicals, Llc Bis(aryloxyalkyl) esters of aromatic polycarboxylic acids and method of preparation
US11407212B2 (en) * 2012-09-21 2022-08-09 Toyo Seikan Group Holdings, Ltd. Packaging material and packaging structure made by using same
US11884777B2 (en) 2018-09-14 2024-01-30 Lg Chem, Ltd. Diol compound, polycarbonate, and preparation method of the same
US12012253B1 (en) 2023-03-02 2024-06-18 Verre Vert, Inc. Lightweight polymer wine bottle suitable for use with natural cork or synthetic stoppers

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1403322A4 (en) * 2001-06-13 2005-12-28 Kao Corp Plasticizer for polyester resin
DE10137505B4 (en) 2001-07-16 2005-06-23 Francotyp-Postalia Ag & Co. Kg Arrangement and method for changing the functionality of a security module
US7820258B2 (en) 2005-10-05 2010-10-26 The Coca-Cola Company Container and composition for enhanced gas barrier properties
US7790077B2 (en) 2006-09-15 2010-09-07 The Coca-Cola Company Pressurized tooling for injection molding and method of using
US8124202B2 (en) 2006-09-15 2012-02-28 The Coca-Cola Company Multilayer container for enhanced gas barrier properties
JP6289865B2 (en) * 2013-10-25 2018-03-07 株式会社Adeka Cellulosic resin composition and film using the same
RU2622413C2 (en) * 2014-11-19 2017-06-15 Федеральное государственное бюджетное образовательное учреждение высшего образования "Кабардино-Балкарский государственный университет им. Х.М. Бербекова" (КБГУ) Polymer composition
JP6582440B2 (en) * 2015-02-25 2019-10-02 Dic株式会社 Cellulose ester resin modifier, cellulose ester resin composition, optical film and liquid crystal display device
CN107428923B (en) * 2015-03-31 2020-03-03 株式会社Adeka Modifier for resin and resin composition using the same
CN110498914B (en) * 2018-05-17 2022-06-03 臻鼎科技股份有限公司 Modified liquid crystal high-molecular polymer, high-molecular film and corresponding preparation method
KR102219311B1 (en) 2018-08-10 2021-02-24 주식회사 엘지화학 Polycarbonate and method for preparing the same
JP7212855B2 (en) * 2018-09-27 2023-01-26 大日本印刷株式会社 Sealing and opening device, tube container, method for manufacturing tube container, and cap

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3516960A (en) 1968-03-18 1970-06-23 Monsanto Co Polyvinyl alcohol compositions with improved oxygen barrier properties
US3575931A (en) 1970-04-06 1971-04-20 Allied Chem Polyethylene terephthalate molding compositions containing dispersible nucleating agents
US3617312A (en) 1968-07-18 1971-11-02 Tee Pak Inc Antimycotic overcoating treatment of cellulose sausage casing
US3951903A (en) * 1974-11-01 1976-04-20 Gte Sylvania Incorporated Modified polycarbonate resin
US4024115A (en) * 1974-10-25 1977-05-17 Basf Aktiengesellschaft Manufacture of polyamide film containing ester of an aliphatic alcohol
US4038250A (en) * 1971-08-25 1977-07-26 Ciba-Geigy Corporation Light protecting agents
US4073775A (en) * 1975-06-12 1978-02-14 Asahi Kasei Kogyo Kabushiki Kaisha Powder coating composition
EP0395237A1 (en) 1989-04-24 1990-10-31 Imperial Chemical Industries Plc Polyester composition
WO1995023063A1 (en) 1994-02-28 1995-08-31 Neste Oy Multilayered polymer films and process for the preparation thereof
US5681906A (en) * 1995-04-19 1997-10-28 Exxon Chemical Patents Inc. Thermoset coating compositions having improved hardness

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59159318A (en) * 1983-03-02 1984-09-08 Teijin Ltd Method for forming film of polyester
JPH01289826A (en) * 1988-05-16 1989-11-21 Teijin Ltd Polyester molding
JPH05169527A (en) * 1991-12-20 1993-07-09 Kanebo Ltd Polyester film with gas barrier properties

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3516960A (en) 1968-03-18 1970-06-23 Monsanto Co Polyvinyl alcohol compositions with improved oxygen barrier properties
US3617312A (en) 1968-07-18 1971-11-02 Tee Pak Inc Antimycotic overcoating treatment of cellulose sausage casing
US3575931A (en) 1970-04-06 1971-04-20 Allied Chem Polyethylene terephthalate molding compositions containing dispersible nucleating agents
US4038250A (en) * 1971-08-25 1977-07-26 Ciba-Geigy Corporation Light protecting agents
US4024115A (en) * 1974-10-25 1977-05-17 Basf Aktiengesellschaft Manufacture of polyamide film containing ester of an aliphatic alcohol
US3951903A (en) * 1974-11-01 1976-04-20 Gte Sylvania Incorporated Modified polycarbonate resin
US4073775A (en) * 1975-06-12 1978-02-14 Asahi Kasei Kogyo Kabushiki Kaisha Powder coating composition
EP0395237A1 (en) 1989-04-24 1990-10-31 Imperial Chemical Industries Plc Polyester composition
WO1995023063A1 (en) 1994-02-28 1995-08-31 Neste Oy Multilayered polymer films and process for the preparation thereof
US5681906A (en) * 1995-04-19 1997-10-28 Exxon Chemical Patents Inc. Thermoset coating compositions having improved hardness

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
International Search Report for PCT/US00/21777 (Equivalent to US 09/634,288), dated Dec. 6, 2000.
Maeda, Y,; Paul, D.R. Effect of Antiplasticiation on Gas Sorption and Transport. II. Poly(Phenylene Oxide), Journal of Polymer Science, Part B, 25, 981-1003, 1987.
Robeson, L.M., The Effect of Antiplasticization on Secondary Loss Transitions and Permeability Polymers, Polymer Engineering and Science, 9, 277-281, Jul. 1969.
Robeson, L.M.; Faucher, J.A., Secondary Loss Transitions in Antiplasticized Polymers, Journal of Polymer Science, Part B, 7, 35-40, 1969.

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050118371A1 (en) * 2002-11-01 2005-06-02 The Coca-Cola Company PET copolymer composition with enhanced mechanical properties and stretch ratio, articles made therewith, and methods
US20050260371A1 (en) * 2002-11-01 2005-11-24 Yu Shi Preform for low natural stretch ratio polymer, container made therewith and methods
US7553441B2 (en) 2003-06-18 2009-06-30 The Coca-Cola Company Polyester composition for hot fill applications, containers made therewith, and methods
US20050100696A1 (en) * 2003-06-18 2005-05-12 Yu Shi Polyester composition for hot fill applications, containers made therewith, and methods
US20050221036A1 (en) * 2004-04-01 2005-10-06 The Coca-Cola Company Polyester composition with enhanced gas barrier, articles made therewith, and methods
WO2006112840A1 (en) * 2005-04-19 2006-10-26 The Coca-Cola Company Polyester composition with enhanced gas barrier, articles made therewith, and methods
US20100098894A1 (en) * 2005-05-11 2010-04-22 The Coca-Cola Company Preforms for preparing lightweight stretch blow molded pet copolymer containers and methods for making and using same
US20060257603A1 (en) * 2005-05-11 2006-11-16 Yu Shi Preforms for preparing lightweight stretch blow molded pet copolymer containers and methods for making and using same
US7572493B2 (en) 2005-05-11 2009-08-11 The Coca-Cola Company Low IV pet based copolymer preform with enhanced mechanical properties and cycle time, container made therewith and methods
US8247049B2 (en) 2005-05-11 2012-08-21 The Coca-Cola Company Preforms for preparing lightweight stretch blow molded pet copolymer containers and methods for making and using same
US20060257602A1 (en) * 2005-05-11 2006-11-16 Yu Shi Low IV pet based copolymer preform with enhanced mechanical properties and cycle time, container made therewith and methods
US7820257B2 (en) 2005-05-11 2010-10-26 The Coca-Cola Company Preforms for preparing lightweight stretch blow molded PET copolymer containers and methods for making and using same
US20060275568A1 (en) * 2005-06-07 2006-12-07 The Coca-Cola Company Polyester Container with Enhanced Gas Barrier and Method
US8545952B2 (en) 2005-06-07 2013-10-01 The Coca-Cola Company Polyester container with enhanced gas barrier and method
WO2007106302A1 (en) * 2006-03-01 2007-09-20 Invista Technologies S.Ar.L. Polymer composition with enhanced gas barrier, articles and methods
US20100044266A1 (en) * 2008-08-22 2010-02-25 E. I. Du Pont De Nemours And Company Polyester Blends
US9359488B2 (en) 2008-12-09 2016-06-07 The Coca-Cola Company Pet container and compositions having enhanced mechanical properties and gas barrier properties and methods
US9464184B2 (en) 2008-12-09 2016-10-11 The Coca-Cola Company Container and composition for enhanced gas barrier properties
US8110265B2 (en) 2008-12-09 2012-02-07 The Coca-Cola Company Pet container and compositions having enhanced mechanical properties and gas barrier properties
US20100143547A1 (en) * 2008-12-09 2010-06-10 Coca-Cola Company Pet Container And Compositions Having Enhanced Mechanical Properties And Gas Barrier Properties
US9051116B2 (en) 2008-12-09 2015-06-09 The Coca-Cola Company Container and composition for enhanced gas barrier properties
US20100143546A1 (en) * 2008-12-09 2010-06-10 The Coca-Cola Company Container and composition for enhanced gas barrier properties
US8685511B2 (en) 2008-12-09 2014-04-01 The Coca-Cola Company Pet container and compositions having enhanced mechanical properties and gas barrier properties
US20120006226A1 (en) * 2009-03-03 2012-01-12 Innogel Ag Starch foils and/or films and a method and use of a device for the production thereof
US9486415B2 (en) * 2009-03-03 2016-11-08 Innogel Ag Starch foils and/or films and a method and use of a device for the production thereof
US11160760B2 (en) 2009-03-03 2021-11-02 Innogel Ag Soft capsule based on starch and a method and device for the production thereof
US10899698B2 (en) 2010-10-26 2021-01-26 Ethox Chemicals, Llc Bis(aryloxyalkyl) esters of aromatic polycarboxylic acids and method of preparation
US8377530B2 (en) 2011-02-08 2013-02-19 Eastman Chemical Company Polyesters with low molecular weight additives for improved gas barrier properties
US20130231422A1 (en) * 2011-09-12 2013-09-05 Girish N. Deshpande Monolayer carbon dioxide barrier pet bottles
US10011714B2 (en) * 2011-09-12 2018-07-03 Plastipak Packaging, Inc. Monolayer carbon dioxide barrier PET bottles
US11407212B2 (en) * 2012-09-21 2022-08-09 Toyo Seikan Group Holdings, Ltd. Packaging material and packaging structure made by using same
US11884777B2 (en) 2018-09-14 2024-01-30 Lg Chem, Ltd. Diol compound, polycarbonate, and preparation method of the same
US10894625B1 (en) 2020-07-29 2021-01-19 Verre Vert, Inc. Lightweight polymer bottle for wine and spirits
US11518569B2 (en) 2020-07-29 2022-12-06 Verre Vert, Inc. Lightweight polymer bottle for wine and spirits
US12012253B1 (en) 2023-03-02 2024-06-18 Verre Vert, Inc. Lightweight polymer wine bottle suitable for use with natural cork or synthetic stoppers

Also Published As

Publication number Publication date
JP4795592B2 (en) 2011-10-19
MXPA02001457A (en) 2002-08-30
ES2262531T3 (en) 2006-12-01
AR025238A1 (en) 2002-11-13
AP2002002394A0 (en) 2002-03-31
PT1204563E (en) 2006-07-31
CN1191972C (en) 2005-03-09
DK1204563T3 (en) 2006-09-04
AP1458A (en) 2005-09-30
JP2003526706A (en) 2003-09-09
BR0013308A (en) 2002-05-28
KR20020029378A (en) 2002-04-18
ATE325048T1 (en) 2006-06-15
IL147523A (en) 2008-03-20
EP1204563B1 (en) 2006-05-03
EA005321B1 (en) 2005-02-24
AU6762700A (en) 2001-03-13
KR100629823B1 (en) 2006-09-29
EA200200250A1 (en) 2002-08-29
WO2001012521A1 (en) 2001-02-22
TR200200382T2 (en) 2002-10-21
DE60027726T2 (en) 2007-05-10
CA2378235A1 (en) 2001-02-22
IL147523A0 (en) 2002-08-14
CN1368929A (en) 2002-09-11
DE60027726D1 (en) 2006-06-08
EP1204563A1 (en) 2002-05-15

Similar Documents

Publication Publication Date Title
US6489386B1 (en) Method and composition for improving gas barrier properties of polymeric containers and films
EP0633911B1 (en) Polyester/polyamide blend having improved flavor retaining property and clarity
EP0857194B1 (en) Polyester/polyamide blend having improved flavor retaining property and clarity
US6319575B1 (en) Polyester resin composition
US6262220B1 (en) Polyester compositions
JP4573060B2 (en) Polyester resin composition and molded article
CN101048275A (en) Polyster-polyamide blends having low haze
US12139600B2 (en) Polymer blends with furan based polyesters
EP0881263A1 (en) Thermoplastic resin compositions containing non-crystalline polyimide
EP2003169B1 (en) Polyester resin composition, method for producing same and molded body
US20100234501A1 (en) Polymer composition with enhanced gas barrier, articles and methods
JP2003113295A (en) Polyester resin composition and molded article
JPS6172051A (en) Polyester composition and container made thereof
JPS61276852A (en) Polyester composition and its use
KR100233156B1 (en) Polyester/polyamide blend having improved flavor retaining property and clarity
JP2570779B2 (en) Polyester hollow molded body
JP2002114892A (en) Polyester resin composition
JPH02198820A (en) Polyester hollow molded item

Legal Events

Date Code Title Description
AS Assignment

Owner name: INVISTA NORTH AMERICA S.A.R.L., DELAWARE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:E. I. DU PONT DE NEMOURS AND COMPANY;REEL/FRAME:015286/0708

Effective date: 20040430

AS Assignment

Owner name: JPMORGAN CHASE BANK, N.A., TEXAS

Free format text: SECURITY INTEREST;ASSIGNOR:INVISTA NORTH AMERICA S.A.R.L. F/K/A ARTEVA NORTH AMERICA S.A.R.;REEL/FRAME:015592/0824

Effective date: 20040430

FPAY Fee payment

Year of fee payment: 4

AS Assignment

Owner name: DEUTSCHE BANK AG NEW YORK BRANCH, AS COLLATERAL AG

Free format text: SECURITY AGREEMENT;ASSIGNOR:INVISTA NORTH AMERICA S.A.R.L.;REEL/FRAME:022416/0849

Effective date: 20090206

Owner name: INVISTA NORTH AMERICA S.A.R.L. (F/K/A ARTEVA NORTH

Free format text: RELEASE OF U.S. PATENT SECURITY INTEREST;ASSIGNOR:JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT AND COLLATERAL AGENT (F/K/A JPMORGAN CHASE BANK);REEL/FRAME:022427/0001

Effective date: 20090206

AS Assignment

Owner name: E.I. DUPONT DE NEMOURS AND COMPANY, DELAWARE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:INVISTA NORTH AMERICA S.A.R.L.;REEL/FRAME:022520/0012

Effective date: 20090407

FPAY Fee payment

Year of fee payment: 8

AS Assignment

Owner name: INVISTA NORTH AMERICA S.A.R.L., NORTH CAROLINA

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:DEUTSCHE BANK AG NEW YORK BRANCH;REEL/FRAME:027211/0298

Effective date: 20111110

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20141203